Treating glauconite



Patented May 1925."

vU INITED STATES PATENT.

1,s3s,z47 OFFICE.

Emma KBIEGSEEIM, or NEW YORK, AND WILLIAM VAUGHAN, or- BROOKLYN,

NEW YORK, ASSIGNORS TO THE POR A'IION OF DELAWARE.

l lo Drawing.

To all whom t't ma concern.-

Be it known t at we, HEINRICH KRIEG- errant, a citizen of the United States, and a resident of New York, in the State of New 5 York, and WILLIAM VAUGHAN, a citizen of the United States, and a resident of Brooklyn, in the State of New York, have invented certain new and useful Improvements in Treating Glauconite, of which the following is a specification.

v This invention relates to treating glauconite; and it comprises a method wherein glauconite is submitted to alternating treatments with li uids containing electrolytes and liquids re atively free therefrom until colloidable fine matter is detachedand removed; all as more fully hereinafter -set forth and as claimed.

Glauconite is the characteristic mineral'of the greensand marls, found in extensive deposits in New J ersey,.Maryland, Virgmia,

reen ranules,

etc. As found, it is in small line c aracter probably of a cryptocrysta and consistin essentially. of a hydrated dou- U ble silicate of iron and potassium. It is of marine'origin and is supposed to be formed,

\ at least to a large extent, as casts in foraminiferousshells; this giving the granule its shape. As it occurs 1n the greensand marl bed, the glauconite' granules are mixed with clay, sand, etc. Sometimes, the amount of the admixture is quite great; sometimes, there is not much impurity. There is, however, alvvays-some admixture of other minerals. The glau'conite granules themselves, when isolated from other accompanying minerals, are not of a-pure character; they are .not unitary and homogeneous and. do

, not consist wholly of the stated characteris- 40 tic green double silicate; there is? other matter present. The exact nature of this forei matter (if it can be so called) is uncer tam. It may, in large part, re resent incom pletely glauconitized materia or de'ca ed glauconite. Or itmay belargely eign matterQ-non-glaucomtm material. Under the-microscope, the green granules are some extent t is foreign matter is apparently a cementing means or matrix holding part1- cles of glauconite' together. Some of the glaueonite granules are composite.

Glaueonite is now usedas a water purify I or less extent, it is tory results in. these respects.

impart at actual orrequires a relatlvely 'seen to carry inclusions and accretions, gent erally of a' rayish' or brownish color. To

rnnmorrr COMPANY, or NEW YORK, N. Y., A con- TREATING onaucom'rn.

Application filed March 27, 1922. Serial No. 547,342. a

.ing material in the so-called zeolite pr0cesses of softening water. In these processes, hard water to be softened is run through a granular bed of materials to which itgives up lime and m'agn sia. After a time, when the bed loses its softening power. to a greater regenerated by passage of After washing, it is again In certain cases, glauconite used in tlns way has advantages over the ordinary zeolites. Being heavier, it is less buoyed by air released from thewater in warming up; it is somewhat less sensitive to slightly acidwaters, such as those sometimes produced in alum processes of clarification, etc. To'enable its use for water purification, the natural glauconite is often simply mechanlcally separated from accompanying minerals, as nearly as may be by various processes and directly used after screening and sizing. In use in water purification, it is desirable that the glauconite granules be clean and free of fines, which would close or impede the channels through the bed. It is desirable to have as little resistance as possible to so the passage of water. It is also, of course, quite undesirable to have the lauconite give any muddiness, turbidity, co or or haziness to assing water.

t is found, however, that clean, granular glauconlte used in its natural condition, in these devices does not always give satisfac- It is apt to:- g ve a turbidity to the water for some time after an installation has been put in service; giv ng up enough finely divided matter to greenish color and haziness'or turb dity to the water. Sometimes this effect lasts for a relatively long period of time. As the'use continues, there is also usually a development of fines or undersize granules. which tend to clog the bed more or less; Often it is necessar after a lapse to interrupt the use of the evioe and get rid of the fine matter clogging the bed. Sometimes it long time for the bed come to what may be called a satisfactory conditlon. These results we have traced to the presence of the stated foreign matter occurring in or on the thely are found in nature. t is the object of the present invention to provide a salt solution. ready for use.

glauconite granules as a of freeing glauconite of this foreign matterand reducing a material free of the noted 0 jections; being stable in the water softening device and not breaking down even after long use and not impartin color or turbidity to the water purified t ereby. The product of this method is com osed of homogeneous and unitary clean-su aced granules, free ofgrayish or brownish spots and having a somewhat increased efl'eetive area; the active glauconi'te being e sad to the passing water at all points. e material is free of decomposed or disintegrable matter. In this method, we take advantage of the difi'erential in the attackabilit o the glauconite proper, that is, the state double silicate, and of the associated minerals which, for the sake of brevity we may here designate as clay, without meaning thereby to im ly any particular chemical composition. this associated mineral is to some extent true clay, but it also contains some material which is near glauconite in composition; being rhaps, as stated, decomposed or decaye glauconite or perhaps material in an arrested state of glauconitization. Pyrites is often present.

Physically, glauconite is not much afiected by contact with saline solutions or solutions containing electrolytes, or by soft water. This, however, is not true of clayey matters generally, or of the foreign matters associated with the glauconite which, in this respect, behave something like clay. Saline solutions convert clay into what is known as a flocculated state and soft water into what is known as the deflocculated condition; a condition in which it is able to form dispersoid suspensions in water. alternating treatment :with' salt solutions and soft water will disintegrate even hard clays (such as shales) and we have found the same to be true with the associated minerals formin part of the natural glauconite granules;

I. act which probably explains much ofthe' trouble in using such natural granules in softening water. In the present invention, therefore, wesimply expose the glauconite granules to such an alternating treatment, washing away in each step the fines produced by disintegration of the associated minerals by the liquids employed.

As the electrolyte solution we may use a solution of common salt or another saline; or acids or alkalies may be used. An alkaline solution of-com'mon salt is advantageous. Ordinary water may be employed in the other phase of the alternation. Operation is usually with the Han ids rather warm; say, at 120 to 150 F. dinarily, a succession of three to five-alternations suflices to produce a material from which fine particles are no longer detached in service. The purioperation may be quickened by a rekmmary treatment witha somewhat aci or s a matter of fact U invention, the whole process may be performed in a single tank, which is best prosomewhat alkaline solution; such as a solu- 'tion containin aluminum sulfate of a weak solution of so ium hydroxid (caustic soda). An alkaline solution of common salt works well. Some acid or alkaline reacting substancemay be mixed with subsequent wash: ing liquids. The washing treatment may be controlled by microscopical examination of the granules and is carried on to a point where the stated adhesions visibly diminish or disappear. As soon as all the fine particles mixed with the coarser grains of glauconite are removed and the forei substances in or on the individual grains have disappeared, the clean material will be suitable for the purpose of the water purification. This stage or condition may be easily determined by a hand lens or by a m1croscope.

- In a practical embodiment of the present vided with a strainer or diaphragm of wire mesh in the bottom. It is often advisable 811 port the glauconite to be treated on this. e glauconite granules in general are quite small and this gravel prevents loss in draining; and it also serves, in connection with the strainer, to ive an even distribution of the'wash liqui s in treatment; these wash liquids being usually sent upwardly through the glauconite. The may or may not be submittedto any of the usual mechanical or magnetic purifying treatments or sized and screened prior to applying the present process. Often this preliminary treatment 1s not worth while, since the present process will take care of any fines and dirt, and also efiects sizing automatically. The first washin treatment is ordinarily with water. The ow may be at the rate of a cubic foot per minute per square foot of the bed. This flow detaches and carries away a large amount of fines; these fines often containin more or less pyrites. The flow may continue for an hour or so; and if economy of water is an object, as 1t often is, the emerging water may be settled in a suitable tank and returned for use anew. In settling, it is often a useful expedient to use a little aluminum sulfate or sulfate of alumina or other coagulant to clarify the water rior to returning it. The temperature of 51c operation may be advantageously 120 to 150 F. Operation may be at room temperature but then requires a somewhat longer time and more water. With the stated rate of flow, the granules of the glauconite bed are lifted more or less, but only the undersized material and fines are carried away. In fting, there is more or less mutual frictiomof the granules and this is probabl useful'in detaching fines and clays. 0 promote glauconite I The greater the amount of preliminary puriabout the "rate stated. The time consumed in; this washing naturally varies somewhat withjthe nature of the material; and, it is generallycontinued until, say,- not more than 1 0 cc. oflmud will. separate out of 500 cc. of wash water on; standing. With average material, about 15 cubic feet of water are required to wash a cubic footof raw glauconite to-this stage of cleanliness. This as, of course, the total amount of water; the

amountwof water. which is run through the bed; but, as stated, the water may be'reused.

fication' of the glaueonite which has been effected (ifflany); the lessis the extent of washing necessary in this stage.

After the washing has gone to the extent desired, the water is out oil and the glauconite allowed to settle and partially drain. In the stratificationeffected in settling, there will be formation of an upper layer of material finer than mesh; thls material being partly fine 'glauconite and partly clay and other minerals. This layer isremoved and discarded, partly because of its impurity and partly because in any event material finer than 60 mesh is not desirable in water soft ening apparatus.- It may, however, be used in various ways (not here important) of producing a synthetic granulated softening material. 4 Because of its glauconite content, the material may be made into a useful fertilizer. Ordinarily, the upper layer differs markedly in color from the next below. Usually, it is gray. It may be shoveled off or otherwise removed. With ordinary glauco'nite having nopre-purification, this layer may amount to as muchlas 10 per cent; that is, out of a charge of, say 200 cubic feet, perhaps, 20 cubic feet will'be found in this top layer. The next operation is to repeat the washing witha solution containing an electrolyte. Ordinarily, we use a common salt solution of 10 Baum or somewhat stronger. With this salt solution may be advantageously -ad mixed acertain amount of caustic alkali.

; Useof alkali hastens the operation. In factories making artificial zeolites by fusion methods, there are generally alkaline liquids,

available which can be used in giving alkalinity to the salt solution. They are .usu

ally hot as produced and the. heat is-utilized.

The flow of salt solution'through the bed of glaueonite may be at the same ratejas that of the water previously used. It is t best sent through in an upward direction.

It conduces to economy of operation to take the salt solution coming from the tank.

above the bed and settle it or filter it and then return it'for passage anew. The salt solution in this stage does not generall detach much fine matter. Its function is to of aluminum sulfate.

- nal material.

. required.

may be blown into the bed or mechanical I place the clay in such a condition that a following water washwill detach and remove it. It ordinarily takes on a greenish color as soon as it contacts with the bed and ner. The green color of the used brine and the matter suspended therein can easily be removed by the addition of small amounts The slight acidity of the brine- (where this is not originally acid or alkaline) produced by the decomposition of the aluminum sultateot'ten appears to be advantageous.

After the passageot the salt solution has 89 been continued as long as is deemed necessary, the residual salt solution is drained away and Washing withwater again ffected in the samemanner as at first. There is again a detaching or productiouot' fine ma- 35 'terial. The wash water running from the bed is usually green at first. This second water washing is continued until 500 cc. separates no more than 5 cc. of mud on settlingj There is once more produced atop 90 stratified layer of fine mud; usually of a more or less gray color. This layer, which is usually quite thin. is mechanically removed, being, for example, shoveled ofi".

The material is next again treated with a 9 salt solution. If the amount of sludge produced in the second water washing was large, it is desirable to continue this second saline treatment for a rather long time; say, for an hour. .Otherwise, a. shorttreatment of half-an-hour or so mostly suflices. Another treatment with fresh water for, say, half-an-hour and then' another treatment with saline solution for some time may follow. v a

The number of these treatments which are required depends altogether on the orig- Three. or four treatments with water and with salt solution may be After the various washings have been effected, we generally remove the glaueonite from the washing vessel by displacement with a strong current of water; thereby r effecting a separation of heavier or overs ze minerals, if any be present. The washed glaueonite maythen be dried in any suit able manner and shipped, stored or used.

In the washing with water and with salt solution in tlie case of dirty materials, it is sometimes advisable to use other methods of stirring orlifting the granules in addition 0 the liquid current. For this purpose, air

stirrers may be employed. ,5

No particular chemical action upon the glauconite by the salt solution is desired in this connection, In so far as it takesplace, however, it is not injurious. Where common salt is the electrolytepmployed, the glaucono" nite takes up sodium in the first passageof brine, but is not thereafter chemically afiected by succeeding passages of brine. In the water washing stage, it is better to use soft 5 water; but if the water is used over and over again, as is usually the case, the glauconite itself will remove hardness.

"On examination under the microscope, raw 'or natural glauconite grains show a rounded shape and a tolerably smooth surface; this surface being of a glassy green color but with numerous areas of grayish or brownish color, these areas being somewhat elevated above the general plane of the surface. These are the material we have called clay. In using such glauconite in softening water, the material in these areas wastes away somewhat,lmt generally does not disappear altogether. It does not seem to have any, or any notable, softening activity; and

gray or brown mineral.

to the extent of its presence it detracts from that of the green mineral which it overlies. Glauconite' grains treated by the present process no longer show the presence of the On shaking with water in a bottle with some degree of energy, there is no detachment either of grayish or greenish matter; nor can such detachment be produced by alternate treatments with I strong salt solution and with water. In

-mass, the material is of a somewhat deeper and purer green than the untreated mineral. In the water purifying apparatus, there is no production of Emuddiness, 'haziness or 2:5 green color; neither is there any production containing, an electrolyte, with collection and removal of fine material separated by and produced in such washings. 2. The process of treating glaucomte which comprises submitting a bed of natural glauconite to a plurality of alternating washings with water and a solution of common salt with collection and removal of fine material separated by.and produced in such washings.

3. The process of treating glauconite which comprises submitting a bed of glauconite to a plurality of alternating wash.

ings with water and an alkaline solution of common salt with removal of fine material separated by and produced in such washings. L p

4. The process of treating glauconite which comprises submitting a bed of glauconite to .a plurality of alternating washings with water and with a solution containing an electrolyte, with removal of fine material separated by and produced in such washings, each washing being discontinued when the fine material removed is not'more than about 5 cc. in 500 cc. of washings.

The process of treating glauconitc which comprises submitting a bed of glauconite to a plurality of alternating wash-.

ings with warm water and with a warm solution containing an electrolyte, with removal of fine material separated by and produced in suclrwashings.

6. The process of treating glauconite which comprises submitting a bed of glauconite to a plurality of alternating washings with water and with a solution containing an electrolyte, the liquids passing the bed being clarified and retransmitted therethrough.

7. The process of treating glauconite which comprises submitting a bed of glauconite to a plurality of alternating washings with water and with a solution containing an electrolyte, the liquid passing the bed being settled and clarified by the use of coagulant chemicals and retransmit-- ted therethrough. Y

8.. The process of treating glauconite which comprises submitting a bed of glauconite to a plurality of alternating washings with soft" water and with a solution containing an electrolyte.

Signed at New York, in the county of New York and State ofNew York, this 21st day of March, 1922.

m INRICH KRIEGSHEIM. WILLIAM VAUGHAN.

CERTIFICATE OF commcnou.

Patent No. 1,538,247. Granted May 19, 1925, m

HEINRICH KRIEGSHEIM ET AL.

It, is hereby certified that error appears in the printed specification of the above numberedpatent requiring correction as follows: Page 2, line 67, for "the word "of" read "or"; .and that the said Letters Patent should be read with thia correction therein that the same may conform to the record of the case in the Patent Office.

Signed and sealed this 29th dayof May, A. D. 1928.

- M. J. Moore, v (Seal) Acting' Commissioner of Patenta. 

